Process for the preparation of a ziegler-natta type catalyst

ABSTRACT

A CATALYST, USEFUL FOR THE POLYMERIZATION OF OLEFINS, WHICH CONTAINS VIOLET TICL3 AND HAS A HIGH STEROSPECIFICITY IS PREPARED BY CONTACTING BROWN TICL3 WITH TICL4 AT A TEMPERATURE BELOW 100*C.

United States Patent U.S. Cl. 252429 A 16 Claims ABSTRACT OF THE DISCLOSURE A catalyst, useful for the polymerization of olefins, which contains violet TiCl and has a high stereospecificity is prepared by contacting brown TiCl with TiCL, at a temperature below 100 C.

BACKGROUND OF THE INVENTION The present invention relates to a process for the preparation of a catalyst and to the method of polymerizing a-olefins by means of the thus obtained catalyst, particularly the method of preparing isotactic polypropylene.

It is well known that titanium trichloride which is used as a catalyst for the polymerization of a-olefins exists in several crystalline forms. Bock and Moser indicate in Monatschefte fur Chemie, 34 (1913), pp. 1825-1843, that by vacuum heating (annealing) at 150 to 200 C., brown TiCl is changed into a violet crystalline species.

Several patents concern the use of the violet form of TiCl obtained by heating brown TiCl at a high temperature, for the polymerization of a-olefins, particularly of propylene, in order to obtain isotactic polypropylene, for example, U.S. Pat. No. 2,951,045, granted to Gamble et al. The violet form of the catalyst is particularly stereospecific for the polymerization of a-olefins, especially for propylene.

As disclosed in French Pat. No. 1,302,808, granted to Montecatini, it is also well known to prepare an olefin polymerization catalyst by reacting with an excess of TiCl, a mineral support which has been impregnated with an organometallic compound, wherein the support is a compound which is soluble either in water or in a solvent used to wash the polymer and then heating this product at a temperature higher than 150 C.

In Belgian Pat. No. 616,930, granted to Hoechst, a process is described for the preparation of a catalyst which comprises mixing at least a stoichiometric amount of TiCl, with organoaluminum compounds, in the absence of a dispersing medium, at a temperature between -30 and 70 C., and heating the reaction mixture thus obtained at a temperature of 100 to 150 C., advantageously at the boiling point of TiCl, (136 C.). According to the examples of this disclosure, the transformation of the brown form of TiCl to the violet form takes place at the boiling point of TiCl These temperatures are the temperatures at which the transformation of the brown crystalline species of TiCl to the violet crystalline species takes place in the absence of TiCl (US. Pat. No. 3,032,511).

SUMMARY OF THE INVENTION Surprisingly, it has been found that a catalyst consisting of violet TiCl is obtained from brown TiCl produced by the reduction of TiCl, at a temperature below about 100 C., by contacting brown TiCl with TiCl According to the invention, a Ziegler-Natta type catalyst which is highly stereospecific is prepared by contactice ing TiCl which is not stereospecific with TiCl, at a temperature below 100 C.

The polymorphic transformation can occur even at room temperature when brown TiCl is kept in contact with TiCl DESCRIPTION OF THE INVENTION The TiCl in the presence of which brown TiCl is transformed into stereospecific violet TiCl at a temperature below 100 C., according to the invention, may be liquid TiCl optionally diluted by an inert diluent, such as a hydrocarbon or gaseous TiCl optionally diluted by inert gases. The TiCL, may be added to brown TiCl after the latter has been washed. The TiCl may also originate from TiCl, used for the preparation of TiCl when an excess of TiCl has been present in the reaction medium or it may be produced during the polymorphic transformation by oxidation of part of brown TiC1 for example, by means of gaseous chlorine.

The brown TiC1 to be transformed may be obtained by any known method, particularly by reduction of TiCl with an organometallic compound.

It must be understood that the catalyst obtained which is called brown TiCl is generally a cocrystallized compound of type 3TiCl .AlCl it is well known that the reduction of TiCl, by an alkylaluminum or by metallic aluminum results in compounds of this type.

A process which is technologically advantageous involves impregnating a support with an organometallic compound and then introducing the thus impregnated support, at room temperature, to an excess of liquid TiCl optionally diluted with an inert diluent. The brown supported TiCl which forms may be separated from the liquid TiCl by filtration, then optionally washed with hexane and dried and finally resuspended in fresh liquid, optionally diluted TiCl in order to eflect the polymorphic transformation of brown TiCl to the violet form byosimple contact with TiCl at a temperature below 10 C.

In a particularly advantageous method according to the invention, supported brown TiCl may be converted directly in liquid TiCL, which is used in excess as the reaction medium; the reaction medium, which contains suspended TiCl and optionally, a diluent is maintained at a temperature below about 100 C. However, in this procedure the concentration of TiCl, should be such that an excess of TiCl, remains after the reduction reaction. When a mixture of TiCl, and an inert solvent is used to convert brown TiCl to the violet form, the concentration of TiCl, should be at least about 5 vol. per volume of solution.

Preferably, the liquid, optionally diluted TiCl in which the transformation takes place is heated to a temperature of about 25 to 100 C. The period of time required for the transformation to take place is a function principally of the temperature, but is also dependent on the dilution of the TiCl and may vary from a few minutes to several hours in the temperature range of 25 to 100 C. Periods of transformation which are too long are of course undesirable from an industrial point of view. In general, the maximum period of treatment is about 100 hours. The time of treatment is preferably chosen between 5 and 45 minutes and preferably between 15 and 30 minutes for temperatures between 40 and C., preferably 60 C. when undiluted liquid TiCl, is used. For treatments at room temperature, 20 to 25 C., a contact time of about 24 hours with undiluted liquid TiCl is necessary. In a general way, the contact time which is necessary for the polymorphic transformation with diluted TiCl, decreases when the temperature increases, whereas the contact time increases with the dilution of TiC1 It has been observed that the activity of the catalyst obtained and the characteristics of polypropylene produced in the presence thereof are better when the temperature of the reduction reaction is regulated so that the TiCl formed is initially brown and the brown TiCl is transformed to the violet form after the reduction reaction takes place with or without separation of the reaction medium from the brown TiCl When the production of polymers having particular physical properties, namely high isotacticities and rigidity moduli, is not of principal importance, the reduction may be carried out by impregnating a support with an organometallic reducing agent and then introducing the thus impregnated support with an excess of TiCl which may be diluted or undiluted, at such a temperature that the reduction of TiCl and the transformation of brown TiCl to a violet form occur simultaneously. Thus, a supported violet catalyst which may be readily separated from the reaction medium by filtration and washing is obtained directly.

As stated above, a preferred embodiment according to the invention involves introducing the support which is impregnated with the reducing agent in liquid TiCl in diluted or undiluted form, transforming the brown TiCl into violet TiCl in the same liquid TiCl, medium at a temperature below the usual transformation temperatures. This is particularly an important technological advantage of the invention. Owing to the presence of a support, it is indeed possible to control the reduction reaction and to carry out this reaction starting from undiluted TiCl and AlEt at room temperature.

However, the reduction reaction may also be carried out in the absence of a support, but the highly exothermal reaction is then very violet and it is necessary to operate at low temperature or in a highly diluted medium using, for example, an inert hydrocarbon as diluent. Operating at room temperature in the presence of a support or at low temperature in the absence of such a support, the reduction reaction may be carried out in pure, i.e. undiluted TiCl, as the reaction medium. The liquid TiCl, in excess in which the reduction reaction has been carried out may then be used as a medium for the transformation of brown to violet TiCl and surprisingly the temperature at which this transformation is effected may be reduced considerably owing to the presence of T iCl From a technological point of view, the possibility of using diluted TiCl is also important, particularly when a non-supported catalyst is desired. As a matter of fact, such a catalyst which is prepared from TiCl and a reducing agent such as an organometallic compound, is obtained at room temperature by carrying out the reducing reaction in an inert solvent capable of dissipating the heat of the highly exothermal reaction. Providing that there is an excess of TiCl, in the inert organic medium in which the TiCl has been formed, the polymorphous transformation of brown TiCl to violet TiCl may be carried out by simple prolonged contact at a suitable temperature of brown TiCl with the solution which has been used for its formation and which contains TiCl, in excess. Owing to the dilution of TiC1 the Washing operations, which are necessary after the polymorphous transformation to eliminate the excess of TiCl are also less numerous.

Among the diluents of TiCl the inert aliphatic hydrocarbons comprising from 5 to carbon atoms which form a liquid mixture with TiCl, under the conditions of polymorphous transformation may be mentioned. Likewise, hydrocarbons which are gaseous under normal conditions of temperature and pressure, but which dissolve in the liquid TiCl may be used. Aromatic hydrocarbons, such as benzene, toluene and xylene are suitable as well.

The polymorphous transformation by means of diluted TiCl, is preferably carried out at a temperature ranging from 40 to 80 0., preferably from 50 to 70 C. At these temperatures, depending on the catalyst type, the polymo p i tra s o ma on time va ies f m ab u /2 hour to several hours, and in certain cases the time may be 12 hours. When a solution of TiCl, containing about 1030% by volume of TiCl is used, for example, at a temperature of about 5070 C., the transformation takes place in about 4 hour to 10 hours.

The use of gaseous TiCL, also has decided technological advantages which stem from the fact that brown TiCl may be transformed readily to violet TiCl without manipulation of liquids, thus without subsequent washing and without requiring the use of annealing equipment at high temperature. Indeed, the brown TiCl which has been washed and dried is simply contacted with gaseous TiCl at a moderate temperature.

The circulation of gaseous TiCl, through pulverulent TiCl may be carried out either by fluidizing the latter with gaseous TiCl which has been optionally diluted with an inert gas such as nitrogen, or by circulating gaseous TiCl which has been optionally diluted with an inert gas in an agitated bed of pulverulent TiCl In general, the vapor pressure of TiCl, under atmospheric pressure and at temperatures below 100 C. is suflicient to transform brown TiCl to violet TiCl The transformation is generally carried out at a temperature ranging from 50 to 100 C., preferably 70 to C. At these temperatures, depending on the type of catalyst, the time of transformation varies from one hour to several days. In general, the contact with gaseous TiCl is maintained between one hour and 48 hours.

The preference is generally given to supported TiCl rather than to non-supported TiCl owing to the fact that polymerization in the presence of catalysts composed of supported TiCl yields polymers which are characterized by better morphology and higher bulk densities.

When brown TiCl supported on a suitable support is heated in an inert hydrocarbon in the absence of TiCl, at a temperature of 60 C., no modification of the color of the catalyst is observed. Thus, it has been discovered that TiCl, specifically enables the transformation of brown TiCl to violet TiCl to take place at a temperature below C.

Polymerization tests of propylene by means of AlEt Cl and a catalyst of brown TiCl heated, e.g. at 60 C. in the absence of TiCl whereby no visible modification of the color of the catalyst occurs. have shown that such a catalyst has very poor activity and the polymers formed thereby are characterized by low crystallinity and a lack of advantageous properties, particularly in comparison to the properties of polymers obtained by means of AlEt Cl and violet TiCl The transformation of the supported catalyst according to the invention to a violet form is thus a good test to determine whether the catalyst which has been treated according to the process of the invention has desirable properties with respect to the polymerization of a-olefins.

The supports used for the preparation of the preferred form of the present invention must be inert or made inert toward the reactants used for the preparation of the catalysts and for the polymerization. Thus, they must not possess active groups, such as hydroxyl groups which are capable of reacting either with transition metal halides or with organic derivatives of aluminum, or, when they possess such active groups, the latter must be present in a sufiiciently low quantity, with respect to those of the other reactants used, that they do not consume a significant amount of the reactants. Organic as well as inorganic supports may be used.

Particularly interesting inorganic supports for the preparation of stereospecific catalysts include: alumina and particularly u-alumina or corundum, silica, aluminum silicates, namely the catalyst supports called silica-alumina and kaolin, magnesium silicates, magnesia, titanium oxide, calcium carbonate, etc.

A particularly interesting application of the process of the invention involves transforming brown TiCl supported on an organic polymer which is inert toward the reactants used during the preparation of the catalyst and during the subsequent activation of brown TiCl to violet TiCl by contact with TiCl, at a temperature below 100 C. In this case also, the TiCl used for the transformation of brown TiCl to violet TiCl may be liquid TiCl undiluted or diluted with an inert diluent or gaseous TiCl optionally diluted with inert gases. It may also be produced during the transformation by oxidation of brown TiCl for example, by means of gaseous C1 The preparation of brown TiC1 may be carried out by any method useful wherein the catalyst is supported on an organic polymer.

The transformation of brown TiCl to violet TiCl at temperatures below 100 C. is particularly useful for catalysts supported on a polymer, since polymeric supports are generally not stable for long periods at temperatures above 100 C.

The process described, e.g. in Belgian Pat. No. 616,930, which comprises mixing an at least stoichiometric quantity of TiCl, with organoaluminum compounds, in the absence of a dispersion medium at 30 to 70 C. and heating the reaction mixture thus obtained to a temperature of 100 to 150 0., preferably at the boiling point of TiCl (136 C.) would not be applicable to TiCl supported on polyethylene or polypropylene, for example, as these polymers swell and degrade at a temperature above 100' C. in the presence of TiCl Violet TiCl supported on an inert polymer constitutes a catalytic system component which is particularly desirable for the polymerization of a-olefins, particularly of propylene, owing to the fact that after calcination, it leaves few ashes, in comparison with a catalyst supported on a mineral support. It is known, indeed, that the ash residue constitutes an important criterion when evaluating polymers. Furthermore, the use of a supported catalyst confers to the catalyst a morphology which allows it to be carried and transported readily; thus, a supported catalyst is easier to use and in addition, the resultant polymer, particularly a polypropylene, has a desirable morphology, excellent free flowing characteristics and a high bulk density.

The presence of a support, moreover, allows the preparation of brown TiCl by a process of reducing TiCl wherein at least one of the reactants, i.e., TiCl or the reducing agent, an alkyl aluminum derivative optionally chlorinated, is dispersed in the support. By means of this procedure, the reaction may be moderated and controlled without resort to solvents and low temperatures. The presence of the support also facilitates the operations of filtering and washing.

In a particularly desirable procedure, the reduction of TiCl is carried out with an organometallic compound at a temperature below 0 C. in the presence of a solid support. The quantities of solid support, TiCl and organometallic compound are chosen so that the reaction mixture remains pulverulent during the entire reaction.

A method for the preparation of TiCl which has substantial technological advantages is disclosed in French patent application No. 6943826 of Dec. 17, 1969 in the name of Solvay et Cie and copending U.S. application Ser. No. 99,720 of Hermans et al. This process involves impregnating a support with such an organometallic compound and introducing it at room temperature to an excess of liquid TiCl optionally diluted with an inert hydrocarbon such as hexane. The supported brown TiCl which forms may be separated from the liquid TiCL; by filtering, then optionally washed with hexane, dried and finally suspended again in fresh TiCl, in order to undergo transformation to the violet form by simple contact with TiCl at a temperature below 100 C.

Before use, the supports must be dried very carefully, either by heating at a temperature of 100 to 400 C. for a sufficient time, or for the supports which are not able to undergo this treatment without degradation (polymers, for example), under vacuum at a lower temperature.

Furthermore, it has been observed that a particular type of inorganic support called a cenosphere, which comprises a porous support in the form of a sphere having an average diameter in the range of 50 to 250 microns and is constituted by small agglomerated elementary particles the diameter of which is in the range of 0.2 to 2 microns, constitutes a support having particularly important advantages in the process according ot the invention.

This type of support is easy to use in the preparation of the catalyst and especially the cenospheres constituted by a-alumina are particularly favorable for obtaining a catalyst having a good morphology and hence, a polymer having also a good morphology.

It must be pointed out also that the use of the supported catalysts obtained by the process according to the invention permits an absolute control of the morphology of the polymer, as described by British Pat. No. 1,162,079 and copending US. application Ser. No. 756,330, filed Aug. 29, 1968, and now US. Pat. No. 3,594,330 a parallelsim is observed between the morphology of the suppolt and that of the polymer. Thus, by an appropriate choice of the support, polymers having excellent morphologies are obtained easily without regard to conditions of preparation of the catalyst itself.

The cenosphere type support may be obtained inter alia by the pulverization (atomization) process, as described in French Pat. No. 1,548,907. The specific surfaces which are disclosed in this patent are generally too high, however, and may be reduced by a more thorough calcination.

Among the polymeric supports, the halogenated polymers are generally not suitable for the process according to the invention as they tend to react with TiCl or with the optionally halogenated alkylaluminum compounds used for the reduction of TiCl and for the activation of violet TiCl Particularly interesting supports for the preparation of stereospecific catalysts which may be used for the polymerization of a-olefins, especially of propylene, are the polymers of a-olefins themselves, i.e. high and low density polyethylenes, polypropylene and poly(4-methylpentene-l). These polymers may be impregnated with an alkylaluminum and TiCl in order to form brown TiCl and then the transformation of brown to violet TiCl in the presence of TiCl at a temperature below C. may be carried out without undergoing modifications which bring about notable effects on the catalyst obtained.

The chemical inertness of the support is determined by impregnating the support with TiCl, at 65 C. and by washing it with dry hexane. The chemical inertness is deemed satisfactory when the support retains in the region of 1 g. of Ti per kg. of support or less.

TiCl, used in the process according to the invention is a pure product obtained by distillation.

As indicated above, an organometallic compound is preferably used as the reducing agent. The organic compounds of a metal of Groups I to III of the Periodic Table of Elements and in particular the organometallic compounds derived from aluminum are particularly advantageous. Among these are found trialkylaluminums, dialkylaluminum halides, alkylaluminum sesquihalides, monoalkylaluminum dihalides, alkylaluminum hydrides, as well as the complex organometallic compounds containing two metals, one of which is aluminum and the compounds obtained by substituting, in the derivatives above, the alkyl groups by cycloalkyl, acyl, arylalkyl or alkylaryl groups.

As to the choice of the organometallic compound used for the reduction, it has been observed that the stereospecificity of the catalysts prepared by means of dialkylaluminum halides and trialkylaluminums increases during heat treatment, but that the catalytic activity decreases for the first compound and increases for the second compound. Preference is generally given to compounds of the second type. However, in general, any organometallic compounds known in the art to reduce TiCl into brown TiCl i.e. organometallic compounds which are sufficiently active to reduce TiCL; at low temperatures may be used in the present process.

A preferred method for preparing the catalyst consists in impregnating the organometallic derivative in a support and introducing it in TiCl which may be undiluted or dissolved in an inert solvent such as hexane. This method allows the preparation of the catalyst in large quantities and thus can be readily extrapolated to an industrial scale.

If the supported organometallic compound is introduced to undiluted TiCl it is not necessary to react the two components in well determined proportions and moreover, owing to the encapsulation of the reactant in the support, i.e. to its presence within the support itself, and not only at its surface, the reaction occurs evenly without having to carefully control the temperature of the medium. Owing to the high specific heat of TiCl the reaction may be carried out at room temperature or above. The reaction may be carried out from about 35 C. (solidification temperature of TiCl to about 100 C. and preferably between and 50 C. The use of TiCL; in excess avoids overreduction to TiCl which has little catalytic activity. Moreover, as mentioned, polymorphic transformation may be carried out immediately at a temperature below 100 C. in the presence of excess TiCl The violet, stereospecific catalyst obtained is used for the polymerization of olefins according to classical methods. Generally, it must be activated by an organometallic compound of a metal of Groups I to III of the Periodic Table. One of the derivatives of aluminum which has been mentioned as a reducing agent of TiCl may be used for the activation. It is possible to use the same compound both for the reduction and the activation, or to use different compounds. Diethylaluminum chloride is a particularly effective activator, as it assures maximum activity and stereospecificty of the catalyst.

The polymerization of a-olefins may be carried out according to any known method:

in the gaseous phase, i.e. in the absence of any liquid medium;

in an inert solvent, preferably a hydrocarbon solvent;

in the monomer itself, kept in the liquid state under its saturated vapor pressure.

The process according to the present invention applies broadly speaking to the polymerization of all the aolefins and more particularly of ethylene, propylene, butene-l, pentene-l, methylbutene-l, hexene-l, 3 and 4- methylpentene-l, long chain a-olefins and styrene. It is particularly interesting for the polymerization of propylene, butene-l and 4-methylpentene-l to crystalline, highly isotactic polymers.

Owing to the high catalytic activity and stereospecificity of the catalysts and particularly of the supported catalysts used, the process according to the present invention allows the simplification and often even the elimination of the step of removing the amorphous fraction of polymer due to its presence in a very low quantity.

The nature of the phenomenon whereby the temperature of polymorphous transformation of brown TiCl to violet TiCl is reduced has not been precisely determined. Comparative tests have shown that catalysts obtained by the reduction of TiCl by means of trialkylaluminum, which, as is it is well known, leads to brown TiCl and AlCl behave differently with regard to the temperature of transformation to a violet form, depending on whether or not the conditions of the invention are respected. The scope of the invention, accordingly, is not limited to a particular crystalline form which may be formed during the treatment according to the invention. X-ray studies of the violet catalyst obtained according to the invenion, however, seem to indicate that it is made of 'y or 6 TiCl The invention will be described in more detail in the following examples among which comparisons are made 8 between catalysts prepared according to the process of the invention and according to conventional methods. The examples of the invention illustrate the best mode currently contemplated for carrying out the invention, but must not be construed as limiting the invention in any manner.

In a first series of examples (1 to 30) processes are described for the polymorphous transformation in the presence of pure liquid TiCl in comparison with heat treatments carried out in the absence of TiCl EXAMPLES l to 19 Catalysts are formed on different supports. The catalysts are treated according to the process of the invention to obtain violet TiCl Moreover, comparison tests are made showing that it is not possible to obtain a violet catalyst in the absence of TiCl when operating below C.

In all the examples, the reaction of formation of TiCl by reduction of TiCL; occurs in an excess of pure TiCl The particular conditions for the preparation of the catalyst and the properties of the catalyst obtained are indicated in Table I.

(1) Impregnation of support Into a glass reactor the inner walls of which are provided with Vigreux tips and which is mounted on a device capable of rotating it, the quantity of support mentioned in Table I is introduced under nitrogen atmosphere, this support having been previously dried for 24 hours at 300 C. under a current of dry nitrogen. As the reactor is rotated, AlEt is added dropwise in such quantity that the support remains pulverulent. AlEt is distributed homogeneously in the support by rotating the reactor or 1 h.

(2) Reduction of TiCl In a cylindrical reactor provided at the bottom with a sintered glass plate, the other reactant is introduced under dry nitrogen atmosphere in the quantities mentioned.

The impregnated support described in (1) is poured in the reactor at the initial temperature indicated and under the conditions mentioned while thermostating the medium.

(3) Heat treatment Heat treatments have been carried out according to the different conditions indicated in Table I.

In Examples 1 to 4, the product of the reduction reaction (2) is separated from TiCl in which it has been prepared, by filtering the suspension through the sintered glass plate with which the reactor is provided. Then it is washed in the same reactor for one or more times with fresh TiCl and finally it is again suspended in fresh TiCl according to the conditions of temperature and time described, in order to effect the polymorphous transformation.

In Examples 5 to 12, the suspension of brown TiCl in TiCL; is also filtered to separate the brown TiCl from the TiCl of the reaction, washed with dry hexane and dried at about 30 C. under reduced pressure to eliminate residual hexane. The brown TiCl is then suspended again in freshly distilled TiCl In Examples 13 to 17, the reduction reaction mixture of TiCL; and suspended brown TiCl is heated with separation of TiCl and TiCl Examples 18 and 19 illustrate the transformation of brown to violet TiCl at room temperature by prolonged contact with an excess of TiCl in Example 18, fresh TiCl is used and in Example 19, the same TiCl from which (and in which) the brown TiCl has been formed by the reduction of TiCl is used.

(4) Properties of resultant catalyst The color of the catalyst obtained has been indicated and an X-ray analysis has been made, in order to determine the crystalline structure of TiCl Polymerization of propylene (a) 1.5 liter autoclave: Into a 1.5 liter autoclave which has been dried and flushed with a flow of gaseous propylene, there are introduced:

200 mg. of Al(C I-I Cl;

the quantity of TiCl indicated in Table I hydrogen under a partial pressure of 1 kg. a./cm. 3 1 liter of liquid propylene.

The temperature of the reaction medium is raised to 60 C. and the reaction mixture is stirred during the time indicated.

The results of the polymerization which were carried out with different catalysts prepared in accordance with the process described in (a) are also set forth in Table I.

(b) 5 liter autoclave: The same procedure is repeated but in the 5 liter autoclave there are introduced:

mg. of

the quantity of TiCl indicated in Table I hydrogen under a partial pressure of 0.7 kg. a./cm. 3 liters of liquid propylene.

The activity and the productivity of the catalyst used has been calculated and on the other hand, the properties of the polymer formed have been measured. The results are also given in Table I.

EXAMPLES TO 28 (1) Preparation of catalyst In a 500 ml. flask provided with Vigreux tips, mounted on an axial rotating device and provided with two axial pipes for the introduction of the reactants, are introduced under an inert atmosphere:

(a) The quantity specified in Table II of a perfectly dried inert support;

(b) then dropwise into the support while stirring, owing to the rotation of the flask, the quantity of AlEt specified, the stirring being maintained until the AlEt has been distributed homogeneously in the support; this operation is carried out at room temperature;

(0) The flask is externally cooled at 20 C. by means of a methanol-solid carbon dioxide mixture and, while rotating the flask, the specified quantity of TiCl is introduced in the flask; as the volumes of the reactants used (AlEt +TiCl are not larger than the porous volume of the support, the latter keeps its pulverulent character before and after reaction;

(d) Without interrupting the rotation of the flask, the temperature is raised to 10 C. in 1 h., then to room temperature also in 1 h.

The brown colored product obtained contains about 200 mg. of TiCl per g. of catalyst.

(2) Heat treatment As for Examples 1 to 19, several heat treatments have been carried out accordingto the conditions specified in Table II.

(3) Properties of the resultant catalyst The results are given in Table II.

(4) Polymerization of propylene Polymerization was carried out according to procedure (a) or (b) as indicated for Examples 1 to 18, the specific conditions and the results are set forth in Table II.

The difierent supports used in Examples 1 to 28, which are commercial products, are described below:

aAl O corundum produced by Carborundum under the trademark SAEHS 33-50 TiO rutile TiO has been used and prepared in the following manner:

A homogeneous paste is formed using a minimum quantity of water. The paste is kept in a ventilated oven (about 100 C.) until apparently dry (1 to 2 h.). The easily friable blocks obtained are introduced into a muflie brought at 950 C. where they stay for about 1 h. 30. Cooling occurs in the air. The tough blocks obtained are milled in a mortar and classified to hold back the particles having from 88 to 250p. (yield about 50%). This support has a cenospheroidal structure.

Calcic fiuoroapatite In a mortar there are mixed 50.232 g. (0.2 mole) of calcic hydroxylapatite [Ca(PO Ca(OH) and 3.904 g. of CaF (0.2 mole). The mixture is kept in a mutfie at 800 C. for 24 h., cooled at 400 C. in the muflle and then the product is introduced in a dessicator.

The product is washed twice with ammonium chloride (2 N) at C. and rinsed with water until the absence of chlorides in the washing water is observed. The paste obtained is introduced in a ventilated oven at C. until apparently dry, then in a muflle at 900 C. (1 hour).

The product obtained is milled and classified, whereby particles of 88 to 250,. are held back.

Being alkaline, the product obtained is treated with 0.1 N HCl and then rinsed with water for several times.

Finally the product is dried in a ventilated oven at 100 C., then in a fluidized bed reactor at 350 C. under nitrogen for 24 hours.

A support is obtained having a cenospheroidal structure (porous volume 0.35 ml./g.).

SiO Silica produced by Avisun is dried in a muflle for 15 h. at 700 C. and then placed in dry nitrogen atmosphere. The porous volume is 1.4 ml./g., 1.9 ml. of AlEt per g. is added, so that it remains pulverulent. Then, the AlEt impregnated silica is extracted with hexane by a Soxhlet. Finally, the silica is dried with dry hexane.

EXAMPLES 29 AND 30 (1) Preparation of the catalyst 250 ml. of pure and dry hexane and 20 ml. of rectified TiCl are introduced under N atmosphere in a 500 ml. three-necked flask, provided with a metallic agitator.

This flask is dipped in a refrigerating bath maintained at a temperature of -40 C. To the solution of TiCl in hexane 10 ml. of pure AlEt are added so as to realize a TiCl /AlEt molar ratio equal to 3. The addition is carried out in 5 minutes and under vigorous agitation.

After the addition, the flask is withdrawn from the bath and left under agitation for 30 min. at room temperature. Then the flask is dipped in a thermostat at room temperature which is raised to 65 C. in 10 min. After agitation for 1 hour at this temperature, the flask is withdrawn from the thermostat and is cooled to room temperature still under agitation.

The flask then contains a suspension of TiCl in hexane. This suspension is decanted under N atmosphere in a filter provided with a sintered plate, in order to separate TiCl from hexane; the TiCl is washed 4 times with 100 ml. of dry hexane and resuspended after each washing.

TiCl is dried under reduced pressure in the filter provided with the sintered plate. For the run above, 36 g. of

TiCl are recovered as a brown pyrophoric powder.

(2) Heat treatment Carried out as indicated in Table II.

(3) Properties of catalyst These properties are also given in Table II.

(4) Polymerization of propylene Carried out as for Examples 1 to 28. The results are given in Table II.

1 1 EXAMPLE s1 (1) Preparation of catalyst One hundred ml. of TiCL, are introduced in a reactor (diameter 65 mm., height 200 mm.), the bottom of which is constituted by a sintered glass plate, provided with a glass helix and with inlet tubes for the reactants. TiCl is cooled at 30 C. and a solution of 10 ml. of AlEt in 20 ml. of dry hexane are added dropwise in 15 minutes.

After the addition, the temperature of the reactor is allowed to rise naturally and reaches 50 C. in about 60 The excess TiCl is removed by filtering through the sintered plate and rinsed 8 times with 100 ml. of hexane. It is dried under reduced pressure. A brown pyrophoric powder is obtained.

(2) Heat treatment Ten g. of this product are suspended in 50 ml. of TiCl The suspension is brought to 40 :C. for 150 min. Then, the product is separated from TiCl by filtration, washed with dry hexane and finally dried.

(3) Properties of the catalyst Set forth in Table H.

(4) Polymerization of propylene The polymerization is carried out as in the preceding examples. The results are given in Table II.

Examples 1 to 4 relate to a process in which the supported brown catalyst, obtained by reaction in pure liquid TiCl is separated from TiCl in which it has been formed, then rinsed one or more times with fresh and undiluted liquid TiCl and finally resuspended in fresh TiCl in order to carry out the polymorphous transformation.

Examples 5 to 12, as well as 18, all relate to a process in which the catalyst, obtained during the reduction, is separated, rinsed and dried before being heat treated.

Heat treatment of Examples 1 to 4 and 9, 11, 12, for a catalyst supported on aAl O and of Example for a 12 catalyst supported on rutile TiO gives a violet catalyst; polymerization of propylene in the presence of this catalyst yields a polypropylene having good properties.

Treatments carried out under conditions which are similar to those of the process of the invention with regard to temperature and time, but in the absence of TiCl (Examples 6 and 7) do not result in a violet catalyst. To obtain the violet form, in the absence of TiCl the classical treatment at 200 C. in dry state or in hexane must be resorted to.

Examples 13 to 17 relates to a process in which the catalyst resulting from the reduction has not been separated, the polymorphous transformation being carried out, except for the comparative examples, in TiCL; which has been used as the reaction medium for the reduction.

Examples 13 to 16 (support, ccA1 O and 17 (support, SiO illustrate the production of violet TiCl by the process of the invention.

From Examples 1 8 and 19, it may be concluded that TiCl in contact with TiCl i.e., TiC1 which has been either separated, rinsed and dried and resuspended in fresh TiC1 or not separated from TiCl which has been used as a reaction medium, becomes violet at room temperature.

'As mentioned, all the catalysts of Examples 1 to 19 have been prepared in an excess of TiCl In Examples 20 to 30, on the other hand, the catalysts have been prepared by reduction of TiCl at low temperature by an approximately stoichiometric quantity of a reducing agent (AlEt In Example 31, the catalyst has been prepared in the absence of a support by reduction at low temperature, by means of a large excess of TiCl Examples 20, 21 and 22 have been carried out according to the invention (supported catalysts) and Examples 23 to 28 illustrate by Way of comparison the classical polymorphous transformation processes.

Examples 29 to 30 provide a comparison of a non-supported catalyst treated according to the invention (30 and 31) with a non-supported catalyst treated according to the classical method (29).

TABLE I Example No 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 1. Impregnation of support:

Nature of support 01211 0 T101 aAlzOz S10 aAlzOa Impregnated support used (g.) 1,500 48 29 50.5 1,500 50 48.5 50 13 1,500 47 AJEt; contentsof support (m1./g.) 0.1 0.116 0.11 0.1 0.11 0.33 0.1 0.1 2. Reduction reaction:

Pure TiCl used (ml.) 3,000 100 3,000 3,000 100 97.5 3,000 100 Intial temperature'( C.) 20 20 20 13 20 20 0 20 20 Time of introduction of solid (min.) 60 5 44 30 38 60 60 43 58 36 30 60 52 Time of reaction after introduction (min) 60 105 30 94 60 60 15 150 25 72 Reactiontemp. C.) 20 25 25 20 15 30 30 30 20 3O 20 25 Rinsing Yes Nature of rinsing solvent- TiCl v Hexane Drying No Yes Yes 3. Heat treatment:

Medium TiCh Hexane TiCl,

Time (min.) 30 15 30 15 6 30 25 15 150 15 120 15 240 15 39 160 30 3 24 9 24 Temperature C.) 60 60 60 60 200 60 60 200 40 100 40 40 60 60 40 40 25 25 4. Properties of catalyst:

TiCl; contents (g./kg.) 176 177 176 153 163 160 160 196 218 225 215 133 257 234 226 232 448 174 172 Reduction rate (mole percent) 94 97 100 Colour Violet Brown Violet X-rays analysis v5 75 76 '16 6 I3 '76 v6 '15 6 v5 5 5. Polymerization:

Polym. condition (a=1.5 liter: b=5

lite b b b b b a b b b b b b a b b T101 used (mg.) 182 173 182 157 170 63 158 148 208 171 170 164 40 161 176 Molar ratio AlEtCl/TiCh.- 4.2 4.5 4.2 4.9 4.5 4 4.9 5.2 3.7 4.5 4.1 4.7 20 4.8 4.4

Polymer time (h.) 3 3 3 3 3 4 3 3 3 3 3 3 3 3 3.5

Product obtairi g (g.) 480 487 480 457 473 480 463 424 455 414 386 100 402 436 Activitym 880 940 880 974 924 542 915 536 1,010 1,043 680 887 741 785 630 831 715 Productivity g. PP/g. sup. eat 465 498 465 446 452 532 598 483 653 416 523 624 502 547 280 433 430 Real density (g./dm. 908 907 908 906 908 905 906 908 907 G modulus 60 arch at 100 C 891 835 891 743 883 782 794 802 772 788 689 767 843 830 848 MFI g./10min. 230 C.under 2.16 kg. 5.6 3.2 5.6 6.9 1.9 2.3 2.7 7 5.8 10.3 3.5 5.5 3.2

1 Hexane.

Hours 3 G m dulu pp tent e y mod lu u d r torsion.

TABLE II Example Nn 20 21 22 23 24 25 26 27 28 29 30 31 1. Preparation of catalyst:

Nature of support fltAlzOa TiOz tAlrOa TiO: aAlzOs Weight of support used (g.) 37 69. 5 61 37 15. 5 72 72 AlEta (ml.) 6.0 6.0 3. 8 5. 8 6.1 3. 8 1. 8 6. 6. 0 10 10 10 TiCh (1111)-- 12.0 12.0 7. 6 11. 6 12.2 7. 6 3. 6 12. 0 12.0 25 25 100 TiClr Hexane TiCli Time (min.) 15 180 6 6 6 15 15 6 15 150 Temperature (3.).-. 80 95 80 140 200 200 200 140 200 200 100 40 3. Proportion of catalyst:

TiCl; contents (g./kg.) 190 190 222 181 203 191 249 6 843 856 735 olor Violet Brown Violet 4. Polymerization:

Polymer conditions (a=1'.5 liter; b-fl 1iter) b b b a a a a a a a a b TiClr used (mg.) 193 157 149 62 56 60 70 48 61 70 58 170 Molar ratio AlEtrCl/TiCl 4 5.0 5. 2 4. 2 4. 6 4. 3 3. 6 5. 4 4. 2 4. 9 4. 4 4. Polymer, time (h.) 3. 5 4 3. 5 3 3 3 3 5 5 3 3 Product obtained (g.) 482 326 257 181 147 187 117 135 165 147 165 407 P Activity 714 520 492 978 866 1,040 417 568 901 566 945 802 'IiClaXh Productiv ity g. PP/g. supp. catal 475 395 382 517 537 596 414 506 614 2, 100 2,430 1, 760 Real density (g./dm. 907 907 907 90 908 907 908 888 908 905 905 G modulus 60 arch at 100 C 857 821 859 821 913 884 898 442 864 771 737 746 MFI g./ min. 230 C. under 2.16 kg 3. 6 5. 8 8.7 8. 9 2.4 2.1 2. 3 6. 9 3.1 3 0 0.73

1 Fluoro apatite.

EXAMPLES 32 TO 37 (1) Preparation of brown TiCl (a) Catalyst supported on aAl O First method A 500 ml. flask, provided with 4 rows of Vigreux tips aligned according to the generants, is mounted on a rotating device provided with inlet tubes for the reactants during the rotation of the flask.

The whole installation is maintained in the dry state 40 and under inert atmosphere. Sixty two g. of uAl O which have been previously dried for 24 h. at 300 C. under a N flow, are introduced into the flask.

The total porous volume of these 62 g. of A1 0 is equal to ml. Five 'ml. of pure AlEt are added dropwise into the flask which is rotated about r.p.m. at room temperature.

The distribution of AlEt in aAl O is made uniform by rotating the flask for 1 to 2 hours.

The flask is externally cooled at -20 C. by means of methanol-solid CO bath during 15 min. Ten ml, recitified TiCl are introduced dropwise into the flask containing alumina which has been impregnated with AlEt still maintained externally at 20 C.

After introduction of TiCl the alumina which has been impregnated with the reaction product of AlEt with TiCl at -20 C., keeps its pulverulent nature.

The temperature of the bath is brought in 1 hour from -20 C. to 10 C.

The support impregnated with brown TiCl is further agitated in the flask for 1 h. at room temperatures.

Second method A 5 l. flask, provided with 14 Vigreux tips, 1 to 2 cm. deep, aligned according to the generants, is mounted on a rotation device provided with inlet tubes for the re- 65 actants during rotation of the flask.

The whole installation is maintained in the dry state and under inert atmosphere.

One kg. of A1 0 which has been previously dried for 24 h. at 300 C. under a N flow is introduced into a flask.

The total porous volume of 1 kg. of uAl O is 280 ml.

A mixture comprising 110 ml. of AlEt and 170 ml. of dry hexane is introduced in 15 min. in a flask which is rotated at about 25 r.p.m. The distribution of the AlEt -hexane solution in aAl O is made uniform by rotating the flask for 1 to 2 h.

In a cylindrical reactor (height 180 mm, diameter 65 mm.), provided with an agitation device and inlet tubes for the reactants, the bottom of which is constituted by a sintered glass plate followed by an outlet tube, 100 ml. of rectified TiCl are introduced under an atmosphere of pure and dry nitrogen.

This reactor is dipped in a thermostat at a temperature of 25 C. and g. of the impregnated support described above are introduced in about 78 min.

After introduction of the total amount of impregnated support into TiCl the medium is further agitated for 94 min. at 25 C.

The liquid phase is then eliminated through the sintered plate and the supported brown catalyst obtained is further washed with 5x ml. of dry hexane. After these washings, the reactor containing the supported catalyst and 100 ml. of hexane is raised to 65 C. for 1 hour, then the supported catalyst is washed again with hexane as above.

The supported brown catalyst is then dried by an upward flow of pure and dry nitrogen through the sintered plate.

(b) Non-supported catalyst.

Third method The process is the same as indicated for Examples 29 and 30.

(2) Polymorphous transformation of brown TiCl The catalysts prepared according to the methods described are then submitted to an identical polymorphous transformation treatment described below:

Brown TiCl is an amount of 4 to 5 g., supported or not, is introduced under N atmosphere in a cylindrical reactor (height mm., diameter 40 mm.) provided with inlet tubes for the reactants, the bottom of which is constituted by a sintered glass plate followed by an outlet tube.

Fifty ml. of a TiCl -n.hexane mixture, having a TiCl content given in Table III are then poured into the reactor containing brown TiCl The reactor is then dipped in an oil bath at 65 C. for a period of time indicated in the table. The violet catalyst obtained is separated from the T iCl -hexane mixture and washed with 100 ml. of dry hexane 5 times through the sintered glass plate, then dried under reduced pressure at 30 C.

(3) Direct preparation of violet TiCl Fourth method Two hundred fifty ml. of pure and dry hexane and 40 m1. of rectified TiCl (Al/T' =0.2) are introduced under N atmosphere into a 500 ml. 3-necked= flask, provided with a metallic agitator.

The flask is dipped in 'a refrigerating bath at -20 C.

Ten ml. of AlEt are added in min. to the solution of TiCl in hexane, maintained under good agitation.

Then the flask is dipped in an oil bath at room temperature, which temperature is raised in min. to 65 C. After agitation for 1 hour at 65 C., the flask is withdrawn from the oil bath and brought back to room temperature, still under agitation.

The flask then contains a suspension of violet TICl in hexane.

This suspension is decanted under N atmosphere in a filter provided with a sintered plate in order to separate the violet TiCl from the solution.

The violet TiCl is washed with 4 times 100 m1. of hexane, then suspended in about 300 ml. of dry hexane.

It is not necessary to separate it from the diluent medium and it may be used by preparing by vigorous agitation, a homogeneous suspension of TiCl in hexane and by sampling, with a graduated pipette, a determined volume of the suspension.

Under the conditions described, 1.5 ml. of the suspension correspond to 243 mg. of TiCl (4) Polymerization of propylene The catalysts obtained have been used for the polymerization of propylene under the following conditions.

In a 5 l. autoclave which has been previously dried and maintained under dry N atmosphere, there are introduced, under a flow of gaseous propylene:

600 mg. of A1Et Cl,

the quantity of TiCl supported or not, indicated in Table III,

hydrogen, under a partial pressure of 0.8 kg. a./cm.

3 l. of liquid propylene.

The temperature of the reaction medium maintained under agitation is raised to 55 C. and kept there for 3 h. The excess of propylene is then eliminated by expansion and the polypropylene formed is recovered.

The properties of the polypropylene obtained are also given in Table III.

l 6 lysts, which are prepared in the brown form by using a stoichiometric ratio of TiCl, and alkylaluminum (Al/Ti-0.4) so that the total amount of reactants is used, and which are then submitted to a second step of polymorphous transformation. It is observed that, at constant temperature (65 C.) an increase of the concentration of TiCL; during the polymorphous transformation permits a reduction of the time necessary to effect the transformation.

The activities of the catalyst are high and products with an excellent rigidity modulus may be obtained thereby.

In a third series of examples (38 to the preparation methods of catalyst and the polymorphous transformation treatments are described in the presence of gaseous TiCI according to the invention. Finally, the results of propylene polymerization runs with catalysts according to the invention are indicated.

EXAMPLES 38 TO 45 (1) Preparation of brown TiCl (a) Catalyst supported on aA1 O First method This method is identical to the first method described in Examples 32 to 37.

Second method This method is identical to the second method described in Examples 32 to 37 (b) Non-supported catalyst.

Third method This method is identical to the third method described in Examples 32 to 37.

(2) Polymorphous transformation of brown TiCl to violet TiCl The reactor used to carry out the transformation of BTiCl to 'yTiCl by means of TiCl vapors comprises a glass cylinder (height 100 mm., diameter 40 mm.) which is separated in two parts by a sintered glass plate.

The volume of the part which is situated above the sin- Polymerization run:

TiCl; used (mg.) Molar ratio AlEt Cl/TiCl; Partial pressure of Hz (kg. absolute/c Polymerization time (h.) Polymerization temperature C.)

Yield of polypripgylene (g.) 353 455 534 470 206 566 o Activlty 750 820 781 704 703 777 h g.TiC a Productivity g. of PP/g. of catalyst 390 524 1,745 1,570 1,572 1,810 Characteristics of polypropylene:

Apparent rigidity modulus under torsion of arch at 100 C. (kg/cm. 833 818 761 742 707 825 MFI at 230 C. under 2.16 kg. g./10 min 8 6.6 4.7 7.1

The analysis of data in Table III indicates that at a concentration of 20 volume percent of TiCL; in hexane, the polymorphous transformation at C. takes place in a short time.

In the case of supported catalysts (Examples 32 and 33), it appears that the method of preparation of the catalyst does not have an important influence on the catalytic properties or on the properties of the polymer obtained with this catalyst.

Examples 34, 35 and 36 relate to non-supported catatered plate is about 3 times superior to the volume of the part situated below the sintered plate.

The reactor is provided with inlet tubes for the reactants above and below the sintered plate. The bottom of the cylinder is constituted by an outlet tube for the liquid reactants.

All the operations are carried out in dry glassware under nitrogen flow. Four to 5 g. of brown TiCl supported or not, are introduced in the part of the reactor situated above the sintered plate.

Liquid TiCl is then introduced in the other part of the reactor so as to bring the level of TiCl to about 1 cm. below the lower part of the sintered plate.

The reactor is then dipped in an oil bath at tempera tures and for times given in Table IV, Examples 38 to (3) Polymerization of propylene The polymerization of propylene is carried out as indicated above in Examples 32 to 37.

v The properties of the polypropylene obtained are also given in Table IV.

(1) Nature of support In Examples 46 to 51, a non-treated polypropylene powder (flufl), prepared by means of a commercial cata lyst, viz. violet 3 TiCl .AlCl (Staufler AA), has been used.

The support (type A) used in. Examples 52 to 56, 63 and 64 is a flufl of polyethylene sold under the name Eltex A1050 by Solvay & Cie.

The support (type B) used in Examples 57 to 59 is a flulf of polyethylene sold under the name Eltex 6037 by Solvay & Cie and obtained by a process involving the use of a partially hexavalent chromium oxide catalyst.

The support (type C) of Examples 60 to 62, 65 and 66 is a flufl of polyethylene obtained by means of a Ziegler type catalyst supported on alumina having a high specific surface.

By fluff is meant a polymer powder as it is obtained immediately at the exit of the polymerization line and having undergone no finishing treatment, e.g. granulation.

(2) Drying of support The support is introduced into a glass flask which is dipped in a bath at 80 C. and subjected to a reduced pressure of 0.1 mm. of Hg for 5 h. The flask is then filled with dry nitrogen under low pressure.

TABLE IV Example No.

Preparation method r 1 -1 1 2 2 3 3 3 Transformation;

Reaction medium gaseous TiCl Contact time catalyst gas us 48 5.5 1 8O 3 48 2.5 1.5 Temperature C.) 24 60 24 24 60 90 Characteristics of catalyst:

Color Violet TiCl; contents (g./kg.) 175 175 178 213 213 745 745 745 Polymerization run:

TiCh used (mg.) 156 163 158 160 188 224 205 276 Molar ratio AlEtzCl/TiCla 5 4.7 4.9 4.8 4.1 3.5 3.8 2.8 Partial pressure H2 (kg. absolute/cm. 0. 8 Polymerization temperature C 55 Polymerization time (h) 3 Yield of polypropylene (g.).- 261 255 387 251 528 g. ofPP Activity-- 563 419 598 544 451 575 408 640 h. g. of T101 Productivity g. of PP/g. of catalyst 296 217 319 348 292 1,287 914 1,428 Characteristics of polypropylene:

Apparent rigidity modulus under torsion at 60 of arch at 100 C. (kg./cm. 756 695 849 918 781 805 792 780 MFI at 230 C. under 2.16 kg. (g./10m1n) 4.5 9.2 6.6 5.5 4.5 4.7 8.5 3

The analysis of the data in Table IV indicates that at (3) Impregnation of support by AlEt or AlEt C1 m erature the times necessar for the tran f 10w te p y S 0mm A flask of 5 liters, provided wrth 14 Vigreux tips, 1 to tion are relatively long.

In the case of supported catalysts (runs 38 to 40 on the one hand, and 41 and 42 on the other hand, it does not appear that the method of preparation of the catalyst can have an important eifect on the catalytic properties and on the properties of the polymer obtained with these catalysts.

Examples 42, 44 and 45 relate to non-supported catalysts which are prepared in the brown form by using a stoichiometric ratio of TiCl and alkylaluminum so that the total quantity of reactants is used. These catalysts are submitted in a second step to eflect the transformation to violet TiCl The activities of the catalysts are high and the products obtained thereby have a good rigidity modulus.

In a fourth series of examples (46 to 66), methods are illustrated for the preparation of catalysts supported on polyolefins, as well as the treatments for the transformation according to the invention.

Finally, the mode of operation is indicated for the polymerization of propylene by means of the catalyst according to the invention. The specific conditions and the results of the diiferent polymerization are given in Table V.

2 cm. deep aligned according to the generants, is mounted on a rotating device provided with inlet tubes for the reactants during the rotation of the flask. The whole apparatus is maintained in the dry state and under inert atmosphere (dry N Nine hundred g. of PP or PE support which has been dried are introduced into the flask.

The quantities of AlEt or AlEt Cl (mL/g.) given in Table V are added dropwise, in 15 min., in a flask which is rotated at about 25 r.p.m. The quantities of liquid introduced are calculated so that the impregnated support keeps its pulverulent character. The distribution of AlEt or AlEt Cl in the support is made uniform by rotating the flask for 1 to 2 h.

(4) Reaction of support impregnated by A1Et or AlEt Cl with TiCl, in excess supported AlEt (Examples 46 to 64) or supported AlEt Cl (Examples 65 and 66) are introduced into the reactor in the times indicated.

After introduction in TiC1 of the complete quantity 20 59 after simple elimination, by filtration, of the TiCl used during the reduction reaction, Without washing with hexane. The transformation of the supported brown TiCl of runs 63 and 64 is carried out respectively in hexane of the impregnated support, the reaction medium is left diluted TiCl and in TiCl; vapor, at the temperatures and under agitation at the temperature and for the times 5 for the times indicated in Table V. indicated. The transformation in gaseous TiCL; medium is carried out in a reactor which is identical to the one used for 5 Transformation of brown TiCl to violet TiCl 3 3 the preparation of supported brown T1Cl is put on the The Catalyst obtained 15 Vlolet the end of the 1 sintered plate and liquid TiCl is introduced under the ceding treatment under the conditions of Examples 51 plate, so as to bring the surface of the liquid TiCl to 1 and 56 and 1t suflices to wash it with h ee h ra to 2 cm. below the sintered plate. Then the temperature room temperature p Or at b g pomt is brought to the temperature indicated. (Example 56), then to dry it.

For runs 46, 50, 5 5 5 5 57 5 0 1 5 and 15 (6) Washing and drying after transformatlon g sg f i i gg gg g zfig zg gfi g The catalysts of Examples 46 and 52 to 66 are washed 3 for the iimes 511: t e emp i indicated with boiling hexane, the others are washed with hexane at room tem erature r n h The transformation of the supported brown T1Cl of then dried flushin g 3 i i g are runs 47, 48, 49 and 62 is carried out in undiluted, pure y g p e a W T'Cl a t' T'Cl r h ti h t 1 an no in 1 4 romt e reac on, at t e emper- (7) p l n f propylene atures and for the times indicated: after havlng successively separated the supported brown TiC1 from TiCl, T Polymerizafion 0f P py Carrled 01111 as of the reaction and having washed the supported brown lndlcated above In Examplfis 32 to 37, the P311131 Pressure TiCl with hexane, the material is dried. The transformaof hydrogen, however, varying from 0.7 to 0.8 kg./cm. tion in pure TiCl is carried out according to Example as indicated in Table V.

TABLE V Example number. 46 47 48 49 50 51 52 53 54 55 56 regnation of support: Nature of support Flufl PP Flufi PE Type A Impregnated support used (g.). 14 12 13. 5 13 31. 5 28. 5 29. 5 34 30 Nature of reactant impregnating the supp lEta AlEt; Impregnating reactant contents of support (mL/g. of supp.) 0. 1 0. 08 0. 1 0.05 Reduction reaction:

Pure TiOli used (ml.) 100 200 Initial reaction temperature C.) 10 +20 +28 ---30 -10 +5 +25 +40 Introduction time of impregnated support in TiClr (min) 20 14 10 12 Reaction time after introduction (min. 92 120 98 32 82 120 180 180 Reaction temperature after introduction C.) 23 40 Washing No Yes No Yes No Yes Nature of washing solvent Hexane Hexane Hexane Drying No Yes No Yes No es Transformation of brown T1013! Reaction medium Liquid T1014 Liquid TiClr Hexane diluent contents of reaction medium (vol. percent) Time (min. 90 30 15 120 150 120 4,300 Temperature C C.) 40 60 40 40 40 23 Washing for 1 h. with boiling hexane Yes No Characteristics of catalyst:

TiCh contents (g./kg. supported catalyst) 159 107 88 131 114 211 74 86 83 48 Reduction rate of Ti (mole percent) 101 104 108 91 96 82 84 Colour \iolet Polymerization:

TiGl; used (mg) r 164 129 167 165 172 167 163 173 171 167 Molar ratio AlEtzOl/TiC 4. 5 4. 7 6 4. 7 4. 7 4. 5 4. 6 4. 8 4. 5 4. 5 4. 6 Partial pressure Hz (kg. aJcmfi) 0.7 0.8 Temperatur 60 55 Weight of product prepared (g.) 291 470 349 379 w 250 494 476 395 361 132 Activity (g. PP/hx g. T1013) 570 958 904 756 490 486 987 976 760 705 264 Productivity (g. PP/g. supported cat.) 272 307 238 297 167 308 218 248 197 38 Characteristics of PP:

Apparent rigidity modulus under torsion at 60 arch at 100 0. (kg./

cm?) 683 624 610 692 496 717 682 718 678 675 536 MFI at 230 C. under 2.16 kg. (g./10 min.) 3. 3 3. 2 3. 7 2. 7 1. 9 6. 9 5.3 8 6. 3 11 10 Example number 57 58 59 60 61 62 63 64 65 66 Impregnation of support:

Nature of support Flufi PE Type B Flufi PE Type C IfIlufi Pf lrll ufl Pg) Y YD Impreg-nated support used (g.) 20 16 24 34 16 Nature of reactant impregnating the supp AlEts AlEta .AlEta AlEtzCl Impregnating reactant contents of support (mL/g. oi supp. 0. 1 0.15 0.15 0.05 0.15 Reduction reaction:

Pure TiCh used (mL) 200 Initial reaction temperature 0.)..- 10 10 +5 10 Introduction time of impregnated sup 14 12 26 12 24 10 10 12 Reaction time after introduction (min.) 75 52 60 60 60 Reaction temperature after introduction 0)"-.- 23 Washing.-. No Yes No Yes Yes No Nature of washing solvent"- T1014 Hexaue Hexane Drying- No No Yes Yes No Transformation of brown T101 Reaction medium Liquid T101 Diluted Gas; Liquid TiCh T1014 T1014 Hexane diluent contents of reaction medium (v01. percent) 50 0 Time (min.) 120 120 360 330 5.400 180 180 Temperature 0.). 40 40 65 65 23 40 65 Washing for 1 h. with boiling hexane Yes Characteristics of catalyst:

TiCh contents (gJkg. supported catalyst) 160 230 142 282 171 61 62. 5 250 237 Reduction rate of Ti (mole percent Cnlmir V Violet TABLE V--Continued Example Number 57 58 50 60 61 62 63 64 65 66 Polymerization:

TiCl used (mg) 180 175 222 174 195 178 179 163 209 224 Molar ratio AlEt2Cl/TiOl:.. 4. 3 4. 4 3. 5 4. 5 4 5 4. 3 4. 7 3. 7 3. 6 Partial pressure H2 (kg. aJcm 0.8 0.7 0.8 0.7 Temperature 55 50 55 55 55 55 55 Weight of product prepared (g.) 557 573 713 258 338 202 210 210 114 00 Activity (g. PP/hx g. T1013) 1,030 1,068 1 1,280 l 594 l 694 380 407 428 1 136 3 100 Productivity (g. PP/g. supported cat.) 495 754 450 418 488 105 74 80 136 131 Characteristics of PP:

Apparent rigidity modulus under torsion at 60 arch at 100 0. (kg./

cm 764 703 764 735 672 500 525 MFI at 230 C. under 2.16 kg. (g./ min.) 2. 7 4. 5 1. 2 3. 4 3. 2 1. 9 5. 6 1. 6 14 1 2.5 hour's running. 2 4 hour's running.

Finally, the application of the catalysts according to the invention to the polymerization of 4-methylpentene-l 1 has been studied.

EXAMPLE 67 In a 5-liter autoclave are successively introduced:

1 liter of dry hexane,

3 ml. of a 200 mg./ml. hexane solution of AlEtgCl,

1.2 g. of TiCl supported on alumina containing 232 mg.

of TiCl g. of catalyst of Example 16.

200 ml. of 4-methylpentene-1.

After having closed the autoclave, a partial pressure of hydrogen of 0.7 kg./cm. is realized and the autoclave is brought to 60 C.

The pressure is then 2 kg./cm.

After a polymerization of 3 hour, 41 g. of crystalline poly(4-methylpentene1) are recovered.

What we claim as new and desire to secure by Letters Patent is:

1. A process for the preparation of a catalyst for the polymerization of olefins having a high stereospecificity and containing violet TiCl which comprises transforming a catalyst component which contains brown TiCl to a stereospecific violet catalyst component by suspending said catalyst component which contains brown TiCl in undiluted liquid TiCl at a temperature below 100 C., said brown TiCl being prepared by reduction of TiCl with an organoaluminum compound.

2. A process according to claim 1 wherein a suspension of said catalyst component containing brown Ti'Cl in said TiCL, is heated for about 5 to 45 minutes at a temperature of about 40 to 80 C.

3. A process according to claim 1 wherein a suspension of said catalyst component containing brown TiCl in said TiCl is heated for about 15 to 30 minutes at a temperature of about 60 C.

4. A process according to claim 1 wherein a suspension of said catalyst component containing brown TiCl in said TiCl, is maintained for about 24 hours at room temperature.

5. A process according to claim 1 wherein the catalyst containing brown TiCl is prepared by reduction with said organoaluminum compound in an excess of TiCl and the transformation of the brown TiCl, is then carried out by maintaining the brown TiCl, in contact with the excess TiCl, in the reduction reaction.

6. A process according to claim 1 wherein said catalyst component which contains brown TiCl is prepared by reacting said organoaluminum compound which impregnates a support with an excess of Ti'Cl in undiluted form.

7. A process according to claim 1 wherein said catalyst component containing brown TiCl is obtained by reaction with said organoaluminum compound in an excess of TiCl and said catalyst component is then separated, washed and transformed into violet TiCl by contact with fresh TiCl 8. A process according to claim 1 wherein said catalyst component is prepared by reduction of TiCl with said organoaluminum compound at a temperature below 0 C., in the presence of a solid support, the quantities of solid support, of TiCL, and of organoaluminum compound being chosen so that the reaction mixture remains pulverulent during the entire reaction time.

9. A process according to claim 1 wherein the T101 is supported by an tat-alumina.

10. A process according to claim 1 wherein the TiCl is supported by an inorganic support comprised of spheres which are constituted by agglomerated particles.

11. A process according to claim 10 wherein the spheres have an average diameter of 50 to 250,17 and are constituted by elementary particles having an average diameter of 0.2 to 2 12. A process according to claim 1 wherein the TiCl is supported by an organic polymer which is inert toward the reactants used during the formation of brown TiCl and during the transformation thereof to violet TiCl 13. A process according to claim 12 wherein the support is polyethylene.

14. A process according to claim 12 wherein the support is polypropylene.

15. A process according to claim 1 wherein said brown TiCl is prepared by reduction of TiCl, at a temperature below 100 C.

16. A process according to claim 1 wherein said catalyst component containing said brown TiCl is contacted with said TiCl at a temperature which is at least ambient temperature.

References Cited UNITED STATES PATENTS 3,594,330 7/1971 Delbouille et al. 26094.9 DA 3,010,787 11/1961 Tornqvist 26094.9 E 3,108,973 10/ 1963 Vandenberg 26094.9 E 3,547,829 12/1970 Lamborn 26094.9 E 3,424,774 1/1969 Tornqvist 26094.9 B 3,153,634 10/ 1964 Thomas 26094.9 DA 3,141,872 7/1964 Nolta et a1 26094.9 B

FOREIGN PATENTS 1,950,755 6/ 1970 Germany.

OTHER REFERENCES Raff et al.: Crystalline Olefin Polymers, vol. XX, Pt. 1, John Wiley & Sons, Inc., New York, pp. -77 (1965).

JOSEPH L. SCHOFER, Primary Examiner E. J. SMITH, Assistant Examiner U.S. Cl. X.R.

252-429 B, 429 C, 441; 260--93.5 S, 93.7, 94.9 B, 94.9 DA, 94.9 E; 42385, 492 

